Detergent composition for hard surfaces



United States Patent 3,248,335 DETERGENT COMPOSITION FOR HARD SURFACES Arthur S. Teot and Dale G. Brown, Midland, M ch, as-

signors to The Dow Chemical Company, Midland,

Mich, a corporation of Delaware No Drawing. Filed Apr. 1, 1965, Ser- No. 444,857

4 Claims. (Cl. 252-161) This application is a continuation-in-part of our copending applications Serial No. 736,001, filed May 19, 1958, now abandoned, and Serial No. 106,520, filed May 1, 1961, now abandoned.

The present invention relates to new and useful detergent compositions. More particularly the present invention relates to hard-surface detergents.

While hundreds of detergents and compositions containing the same are known to the art, very few have the properties which sucessfully clean hard-surface articles such as dishes and glasses. With the advent of the machine dishwasher even fewer detergents have been found with the ability to remove, adequately, food particles and to give a clean water-break under machine conditions. Several of the detergents formerly acceptable foam excessively in the machine washers because of the water pressures employed. Others lose their foam stability. Attempts to reduce the foaming with anti-foam agents and to stabilize the low foamers have not been entirely satisfactory. Therefore, it would be desirable to have a de tergent useful in both machine washers and the kitchen sink which gives clean water-break, good food removal and regulated foaming. Such a detergent has been found in Z-Qctadecyldiphenyl oxide disulfonate. When this detergent is incorporated into the alkaline inorganic salt builders of the present day hard-surface detergents a superior detergent composition i provided. It also has been found that the substitution of as little as by weight of the detergent compound of compositions containing alkylaryl sulfonate or alkylaryl polyether detergents, with the 2-octadecyldiphenyl oxide disu-lfonate will markedly improve the resulting compositions food removal and water-break properties and lower the foaming to a useful level for machine dishwashers.

The new compound can be prepared by reacting an aliphatic alcohol with a diphenyl oxide in the presence of aluminum chloride at temperatures of from 40 to 150 C, in the manner of US. Patent No. 2,555,371 and/or 2,170,989 and subsequently sulfonating the alkylated compound in the manner of US. Patent No. 2,584,477, issued Septembmer 30, 1958. The compound has at least one 2- octadecyl radical and between 1.8 and 2.5 sulfonate radicals per diphenyl oxide molecule.

The new compound can be successfully compounded or formulated with substantially any of the known auxiliary ingredients, i.e., builders, of hard-surface detergents. I

It is to be further understood that certain of the well known detergents heretofore employed in combination with the alkaline inorganic salt builders can be markedly improved by substituting a portion from 10 to 90% by weight thereof with the active ingredient of the present invention. The two classes of detergents which show marked improvement are the alkali metal salts of the alkaryl sulf-onates and the alkaryl polyethers. Representative of the first class of compounds are sodium dodecylbenzene sulfonate, potassium isopropylnaphthalene sulfonate, sodium nonylbenzene, sulfonate and the like. Representative members of the alkaryl polyethers are nonylphenol-9 moles ethylene oxide condensate, octylphenyl condensed with 8-9 moles of ethylene oxide, dodecylphenol-10 moles ethylene oxide condensate.

as sodium tripolyphosphate, chlorinated trisodium phos- Patented Apr. 26, 1966 phate, sodium carbonate, sodium metal-silicate, mixtures of the same, and the like with Z-octadecyldiphenyl oxide sodium sulfonate alone as Well as with various of the alkylaryl sulfonates or the alkylaryl polyethers.

Typical formulations of hard-surface detergent compositions useful in present day machine dishwashers are set forth below. Percentages are calculated on an anhydrous basis.

Percent Grams y weight Na tripolyphosphate 14. 4 64 Na, metasilimte 7. 7 34. 2 Surfactant 1 O. 14 1. 8

N3, metasilimte 7. S 52 Na tripolyphosphate 4.8 1 32 Ethylenediamine tetraacetic acid tetrasodium salt 1. 2 8 Surfactant 1 1. 2 8

III

Na tripolyphosphate 14.45 65. 7 Na metasilio'ite 7, 5 34 2 Surfactant 0. 022 0. l

1 The surfactant can be employed as a binary mixture of from 10 to by weight of one surfactant and the balance a second surfactant.

In formulations such as set forth above it has been found that the surfactant of the present invention can be employed in from 0.1 to 12% and preferably from 1 to 8% by weight of the total formulation and that it may be used to replace all or any. portion of the alkylaryl sulfonates or alkylaryl polyether detergents.

The following examples illustrate the present invention but are not to be construed as limiting.

Example 1 Chinaware plates each smeared with A of a soft boiled egg per plate were allowed to stand in the air for two hours until dry. A household automatic dishwashing machine having a volume of 2% gallons capacity, a 5- minute wash cycle, tWo l-minute rinse cycles and a 23- minute drying period was employed using 22.5 grams (anhydrous basis) of formulation 11 above using various surfactants as the active ingredient. The incoming water was at 161 F. and had a hardness of 67 p.p.m. as CaCO The detergency effect of each of the surfactants is tabulated below:

A numerical rating scale was arbitrarily selected as follows:

5.0=all egg off; clean on Water-break 4.5:all egg 01f; 50% clean on water-break 4.0=all egg off; 50% clean on water-break 3.5=1 egg spot 3.0=24 egg spots 2.0:5-10 egg spots 1.0:11-20 egg spots 0= 20 egg spots The following table sets forth the average of the data obtained by washing two egg-soiled plates under the above conditions. In the binary mixtures, 0.6 gram of one surfactant and 0.6 gram of a second surfactant was used. The table below shows the data obtained using the various detergent combinations. Thus A-A, the intersection of the horizontal A line over the vertical A column, is sodium dodecyldiphenyl oxide disulfonate, AD is 50-50 mixtures of sodium dodecyldiphenyl oxide sulfonate and polyethylene glycol-polybutylene oxide condensate.

Detergent Detergent:

Example 2 Tests were made to compare the performance of a number of surfactants for removing dried milk from clear glass tumblers in hard water. The following formulation was used:

Grams Na ortho silicate 14.4 Chlorinated trisodium phosphate 2.4

Victamide (an amido-polyphosphate sequestrant made by Victor Chemical Works under US. 2,112,112) 2.4

Surfactant 0.8

The glasses were prepared for the washing test by emptying out homogenized whole milk rotating the glassespurposely leaving as much milk as possible on the glasses. The four coated glasses were then placed in a convection oven at 6085 C. After 2-3 minutes the glasses were removed, rotated to spread the milk over the sides again and replaced in the oven. This was repeated until the water had all evaporated with the maximum time being around minutes. A hard water was made synthetically by adding Ca and Mg chlorides (2:1 ratio) suificient to raise city tap water of 67 p.p.m. hardness as CaCO to about 300 p.p.m. hardness. Water temperature was 160 F. The results of the washing test in a commercial home spray type dish washing machine are tabulated below. To allow statistical treatment of the data, a numerical rating system was devised.

1=Crystalclean with no more spots than one would get by washing a clean glass with distilled H O.

2=Slight hint of haze.

3=Clean with a large number of milk spots or a light hazy film covering the glass..

4=Thick hazy film or milk streaks.

4 Example 3 In the manner described in Example 2 above using city tap water (78 p.p.m.) and four drinking glasses coated with milk (dried as described above) and cleaning formulations below additional tests were made to show the superiority of the detergent of the present invention even in amounts as small as 1%. The same rating system as employed in Example 2 was also employed in this example.

CHANGING FORMULATIONS Percent Sodium tripolyphosphate 65.7 Sodium meta silicate 34.2 Surfactant .1

.1% a-METHYL HEPTADECYL DIPHENYL OXIDE DISULFONATEMILK REMOVAL RATING Glass:

Average 1.5

.1% SODIUM DODECYL DIPHENYL OXIDE DISULFO- NATE MILK REMOVAL RATING -2-octadecyldiphenyl oxide disulfonate.

2. A hard-surface detergent composition consisting essentially of alkaline inorganic salt builders and from 01 to 12% by weight of a binary detergent mixture of from 10 to by weight of sodium 2-octadecyldiphenyl oxide disulfonate and 90 to 10% by weight of a surfactant selected from the group consisting of an alkylphenol con-.

densed with ethylene oxide, alkali metal alkylbenzene sulfonate and alkali metal alkylnaphthalene sulfonate.

3. A hard-surface detergent composition consisting es- Drops of p.p.m. Avg. rating Surfactant D-C 1 anti- Hard- Appearance of 4 foam A to ness replicates kill foam None 0 308 All glasses clear with a large number of spots 3 2-Octadecyldiphenyl oxide disulfonate.-.. 1 308 Three glasses were clear with 10 spots. One 1 glass had a slight tint of haze. Na dodecylbenzene sulfonate 4 312 Three glasses were clear with over 200 spots 3 and the other had milk left. 3 281 All clear with over spots 3 6 29s Slight hint of haze with 1-2 spots 2 4 318 Clear with high number of spots 3 10 310 Clear glass. milk-streaked with 50 spots. Fllm 3 of haze with 12 spots. Fairly clear with 100 spots.

1 Silicone antifoam manufactured by Dow-Corning Corporation.

2 A commercial surfactant containing as the major active ingredient a polypropylene oxide-ethylene oxide condensate.

5 A commercial surfactant containing as the major active ingredient octylphenol-ethylene oxide condensate. 4 A commercial surfactant containing as the major active ingredient N-octa decyl tetrasodium (1,2-dicarboxyl ethyl) sulfosuccinaate.

5 A commercial surfactant containing as a major ingredient sodium lauryl sulfate.

sentially of alkaline inorganic salt builders and from 1 to References Cited by the Examiner 12% by weight, based on the composition, of sodium UNITED STATES PATENTS 2-octadecyldiphenyl oxide diSdlfOnate. 2 0 1 7 5 37 Prahl 260 150 4. A hard-surface detergent composition consisting es- 6 2,477,383 7/ 1949 Lewis 252-161 sentially of alkaline inorganic salt builders and from 1 to 2,854,477 9/1958 stelllhauer 2605 12 12% by weight of a binary detergent mixture of from 10 2990375 6/1961 stemhauer et a1 252 138 to 90% by Weight of sodium Z-octadecyldiphenyl oxide OTHER REFERENCES disulfonate and 90 to 10% by Weight of a surfactant se- Schwartz et al.: Surface Active Agents, Interscience lected from the group consisting of an alkylphenol con- 10 Publishers 1949: P- 122-126- densed with ethylene oxide, alkali metal alkylbenzene JULIUS GREENWALD Primary Examiner sulfonate and alkali metal alkylnaphthalene sulfonate. 

1. A HARD-SURFACE DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF ALKALINE INORGANIC SALT BUILDERS AND FROM 0.1 TO 12% BY WEIGHT, BASED ON THE COMPOSITION, OF SODIUM 2-OCTADECYLDIPHENYL OXIDE DISULFONATE. 